CN104925750B - A kind of TiO with Yolk-Shell structure2nano wire-Ag/AgCl-Fe3o4the preparation method of composite - Google Patents
A kind of TiO with Yolk-Shell structure2nano wire-Ag/AgCl-Fe3o4the preparation method of composite Download PDFInfo
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Abstract
The invention discloses a kind of TiO with Yolk Shell structure2Nano wire Ag/AgCl Fe3O4The preparation method of composite, comprises the following steps: (1) utilizes hydro-thermal method at Ti sheet surface finish nano TiO2Nano wire；(2) modification TiO prepared by liquid phase reduction preparation process (1) is utilized2Modify AgNP further on the Ti sheet of nano wire, obtain modifying nano-TiO2The Ti sheet of nano wire AgNP；(3) nano-TiO will be modified with immersion method2The Ti sheet of nano wire AgNP is immersed in ferric chloride in aqueous solution, obtains nano-TiO2Nano wire Ag/AgCl Fe3O4Composite.The preparation method needed raw material of the present invention enriches, low cost, produces without garbage, and preparation technology is simple, reproducible.Prepared composite has a wide range of applications at aspects such as photocatalysis, gas sensitive, anti-biotic materials.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly relate to the preparation method of a kind of composite, more particularly to a kind of TiO with Yolk-Shell structure2Nano wire-Ag/AgCl-Fe3O4The preparation method of composite.
Background technology
In nano materials research field, nanoscale TiO2The appearance of material has landmark meaning undoubtedly.Nano-TiO2There is the advantages such as photo-catalysis capability is strong, chemical stability good, anti-light corrosion, safety is nontoxic, non-secondary pollution, cost are the highest, raw material is easy to get, can be used for the numerous areas such as air cleaning, sewage disposal, photolysis water hydrogen, antibacterial, antifogging self-cleaning, solaode.But TiO2Greater band gap (3.2eV), the ultraviolet light that wavelength is only less than or equal to 387.5nm has absorption, this utilizes solar energy to it, and (ultraviolet light only accounts for 3%-5%, visible ray accounts for 43%) the actual application that carrys out photocatalytic pollutant degradation constitutes a huge obstacle. and noble metal nano particles has the characteristic to visible absorption because of surface plasmon resonance effect, utilizes this characteristic noble metal nano particles can be prepared as plasma photocatalysis agent.Wherein more as the research of plasma photocatalysis agent with Ag and Ag/AgX (X=Cl, Br, I) nano material.Due to tunability and the multifunctionality of core void shell structure, Yolk-shell nanostructured can be that the aspects such as nanocatalyst, micro-reaction and drug delivery provide powerful platform.At functional material, catalysis, multiple fields such as medical and biological, Fe3O4Have a wide range of applications, and closely bound up with its structure.Therefore, regulation and control Fe3O4Structure to Fe3O4Actual application there is decisive role.By coordinating TiO2-Ag/AgCl-Fe3O4Mutual effect, inquire into its performance and widen his use field.Therefore, utilize simple method, prepare TiO2-Ag/AgCl-Fe3O4Composite is significant.
Summary of the invention
Goal of the invention: for solving problems of the prior art, the present invention provides a kind of TiO with Yolk-Shell structure2Nano wire-Ag/AgCl-Fe3O4The preparation method of composite, the method low cost, simple to operate, different morphologies is controlled.
Technical scheme: for realizing above-mentioned technical purpose, the TiO with Yolk-Shell structure of the present invention2Nano wire-Ag/AgCl-Fe3O4The preparation method of composite comprises the following steps:
(1) utilize hydro-thermal method at Ti sheet surface finish nano TiO2Nano wire；
(2) modification TiO prepared by liquid phase reduction preparation process (1) is utilized2Modify AgNP further on the Ti sheet of nano wire, obtain modifying nano-TiO2The Ti sheet of nano wire-AgNP；
(3) nano-TiO will be modified with immersion method2The Ti sheet of nano wire-AgNP is immersed in ferric chloride in aqueous solution, obtains nano-TiO2Nano wire-Ag/AgCl-Fe3O4Composite, then drying for standby.
Specifically, in step (1), modify nano-TiO2The step of nano wire is: modify nano-TiO2The step of nano wire is: the Ti sheet of 0.15～0.3g is put in acetone ultrasonic 10～15min, then obtains cleaned Ti sheet with distilled water flushing 3～4 times；The NaOH solution that 15～25mL concentration are 1～2mol/L is joined in polytetrafluoroethyllining lining autoclave, then cleaned Ti sheet is put in above-mentioned NaOH solution, autoclave is sealed and is placed on and the baking oven of 220～240 DEG C reacts 8～10h；Reaction takes out Ti sheet after terminating, and with distilled water flushing 2～4 times, and puts in drying baker and is dried, i.e. obtains and modify TiO2The Ti sheet of nano wire.Preferably, the temperature being dried is 50～70 DEG C.
In step (2), the step of liquid phase reduction is: the silver nitrate solution of compound concentration 0.05mol/L, precipitating postprecipitation disappears to make it occur with the ammonia regulation silver nitrate solution that volume fraction is 2%, i.e. silver ammino solution, modification TiO step (1) obtained2The Ti sheet of nano wire reacts 0.5～1h in being immersed in described silver ammino solution and being placed on the water-bath of 60～70 DEG C；Reaction takes out Ti sheet after terminating, and with distilled water flushing 2～4 times, can modify TiO on Ti sheet2Nano wire@AgNP.
In step (3), TiO will be modified2The Ti sheet of nano wire-AgNP is immersed in ferric chloride in aqueous solution 2～3h, and reaction is taken out after terminating, and with distilled water flushing 3～4 times, is then placed in drying baker being dried.Preferably, the temperature being dried is 50～70 DEG C.
Beneficial effect: the present invention utilizes simple material, such as raw materials such as titanium sheet, ethanol, silver nitrate, ammonia, iron chloride, uses hydro-thermal method, liquid phase reduction and immersion method successfully to prepare TiO2Nano wire-Ag/AgCl-Fe3O4, there is yolk-shell structure, and hollow part controllable on titanium dioxide nano thread surface in composite.The preparation method needed raw material of the present invention enriches, low cost, produces without garbage, and preparation technology is simple, and reproducible, prepared composite has a wide range of applications at aspects such as photocatalysis, gas sensitive, anti-biotic materials.
Accompanying drawing explanation
Fig. 1 is TiO of the present invention2The SEM figure of nano-material；
Fig. 2 is the TiO of variable concentrations iron chloride of the present invention2Nano wire@Ag*NP@void@Fe3O4The SEM figure of nano composite material；Wherein:
A () is the TiO being not added with iron chloride2Nano wire@AgNP；
B () is the TiO adding ferric chloride solution 1 (10mL water+10uL1.0mol/L ferric chloride solution)2Nano wire@Ag*NP@void@Fe3O4Nano composite material；
C () is the TiO adding ferric chloride solution 2 (10mL water+30uL1.0mol/L ferric chloride solution)2Nano wire@Ag*NP@void@Fe3O4Nano composite material；
D () is the TiO adding ferric chloride solution 3 (10mL water+50uL1.0mol/L ferric chloride solution)2Nano wire@Ag*NP@void@Fe3O4Nano composite material；
Fig. 3 is the TiO of variable concentrations presoma of the present invention2Nano wire@Ag*NP@void@Fe3O4The XRD figure of nano composite material；
Fig. 4 is the TiO of variable concentrations presoma of the present invention2Nano wire@Ag*NP@void@Fe3O4The TEM figure of nano composite material；Wherein (a) is the TiO being not added with iron chloride2Nano wire@AgNP；B () is the TiO adding ferric chloride solution 12Nano wire@Ag*NP@void@Fe3O4Nano composite material；C () is the TiO adding ferric chloride solution 22Nano wire@Ag*NP@void@Fe3O4Nano composite material；D () is the TiO adding ferric chloride solution 32Nano wire@Ag*NP@void@Fe3O4Nano composite material；
Fig. 5 is the TiO of variable concentrations presoma of the present invention2Nano wire@Ag*NP@void@Fe3O4The EDX figure of nano composite material；Wherein (a) is the TiO adding ferric chloride solution 12Nano wire@Ag*NP@void@Fe3O4Nano composite material；B () is the TiO adding ferric chloride solution 22Nano wire@Ag*NP@void@Fe3O4Nano composite material；C () is the TiO adding ferric chloride solution 32Nano wire@Ag*NP@void@Fe3O4Nano composite material.
Detailed description of the invention
The invention provides a kind of TiO with Yolk-Shell structure2Nano wire-Ag/AgCl-Fe3O4(it is also indicated as TiO in the text2Nano wire@Ag*NP@void@Fe3O4) preparation method of composite, comprise the following steps:
(1) nano-TiO is prepared by hydro-thermal method2Nano thread structure:
The Ti sheet of 0.15g is placed on equipped with 15min ultrasonic in the beaker of acetone, then uses distilled water flushing 3 times；The NaOH solution that 20mL concentration is 2mol/L is joined in polytetrafluoroethyllining lining autoclave, then cleaned Ti sheet is put in NaOH solution, autoclave seals and is placed on reaction 8h in the baking oven of 240 DEG C；Reaction takes out Ti sheet after terminating, and with distilled water flushing 3 times, and puts in drying baker and is dried, i.e. obtains and modify TiO2The Ti sheet of nano wire.Fig. 1 is TiO2Nano wire scanning electron microscopic picture, sees that from figure the nanowire size obtained is homogeneous；
(2) nano-TiO is prepared by liquid phase reduction2Nano wire@AgNP structure.
The silver nitrate solution of configuration 20mL concentration 0.05mol/L, precipitating postprecipitation disappears to make it occur with the ammonia regulation silver nitrate solution that volume fraction is 2%, i.e. silver ammino solution；0.5h is reacted in the Ti sheet of above-mentioned modification being immersed in silver ammino solution and being placed on the water-bath of 60 DEG C；Reaction takes out Ti sheet after terminating, and with distilled water flushing 3 times, i.e. obtains and modifies TiO2 nano wire@AgNP on Ti sheet.TiO in Fig. 32The XRD figure sheet display sheet of nano wire@AgNP, peak correspondence TiO in the product obtained2Nano wire, the crystal face of Ag, occur without other miscellaneous peaks, illustrate that product is TiO2Nano wire and the composite of Ag.Fig. 2 a and Fig. 4 a is respectively TiO2Nano wire@AgNP scanning electron microscope and projection electron microscopic picture, see that from figure obtaining silver nano-grain modifies uniformly at TiO2On nano wire, silver nanoparticle size is about 30nm；
(3) nano-TiO is prepared by immersion method2Nano wire@Ag*NP@void@Fe3O4(can also be written as
TiO2Nano wire-Ag/AgCl-Fe3O4) structure.
Wherein, Ag* represents-Ag/AgCl mixture, Ag and AgCl mol ratio can be according to the time-controllable soaked in ferric chloride solution in the range of 1: 10～10: 1 ,-Fe simultaneously3O4The thickness of layer can be adjusted between 1～20nm.
TiO will be modified2The Ti sheet of nano wire@AgNP is immersed in the ferric chloride in aqueous solution of 10mL variable concentrations:
Ferric chloride solution 1:10mL water+10uL 1.0mol/L ferric chloride solution；
Ferric chloride solution 2:10mL water+30uL 1.0mol/L ferric chloride solution；
Ferric chloride solution 2:10mL water+50uL 1.0mol/L ferric chloride solution；
Immersion time 2h, reaction takes out after terminating, and with distilled water flushing 3 times, and puts in drying baker and is dried, i.e. obtains TiO2Nano wire@Ag*NP@void@Fe3O4Nano composite material.It is illustrated in figure 2 the TiO of variable concentrations iron chloride of the present invention2Nano wire@Ag*NP@void@Fe3O4The SEM figure of nano composite material.XRD figure sheet in Fig. 3 is (except TiO2Nano wire@AgNP is outer) display, peak correspondence TiO in the product obtained2Nano wire, the crystal face of Ag, AgCl, illustrate that product is TiO2Nano wire, the composite of AgCl and Ag.Picture in Fig. 5 shows, unit corresponding in the product obtained have: Ag, Fe, Ti, Cl, O (other are the reasons due to test condition), and the oxide (Fe in composite with ferrum is described3O4).Fig. 2 b-c and Fig. 4 b-c is respectively the TiO of variable concentrations presoma2Nano wire@Ag*NP@void@Fe3O4Nano composite material scanning electron microscope and projection electron microscopic picture, see obtaining modifying yolk-shell structure, and hollow part controllable occur on titanium dioxide nano thread surface from figure, increase along with the concentration of presoma, Fe simultaneously3O4The thickness of layer can be adjusted between 1～20nm.
In sum, the present invention utilizes simple material, such as raw materials such as titanium sheet, ethanol, silver nitrate, ammonia, iron chloride, uses hydro-thermal method, liquid phase reduction and immersion method successfully to prepare TiO2Nano wire-Ag/AgCl-Fe3O4, there is yolk-shell structure, and hollow part controllable on titanium dioxide nano thread surface in composite.The preparation method needed raw material of the present invention enriches, low cost, produces without garbage, and preparation technology is simple, and reproducible, prepared composite has a wide range of applications at aspects such as photocatalysis, gas sensitive, anti-biotic materials.
Claims (5)
1. a TiO with Yolk-Shell structure2Nano wire-Ag/AgCl-Fe3O4The preparation of composite
Method, it is characterised in that comprise the following steps:
(1) utilize hydro-thermal method at Ti sheet surface finish nano TiO2Nano wire；
(2) modification TiO prepared by liquid phase reduction preparation process (1) is utilized2The Ti sheet enterprising one of nano wire
Step modifies AgNP, obtains modifying nano-TiO2The Ti sheet of nano wire-AgNP；
(3) nano-TiO will be modified with immersion method2The Ti sheet of nano wire-AgNP is immersed into ferric chloride in aqueous solution
In 2～3h, reaction is taken out after terminating, and with distilled water flushing 3～4 times, obtains nano-TiO2Nano wire
-Ag/AgCl-Fe3O4Composite, then drying for standby.
Preparation method the most according to claim 1, it is characterised in that in step (1), modifies nanometer
TiO2The step of nano wire is: the Ti sheet of 0.15～0.3g is put in acetone ultrasonic 10～15min, then uses
Distilled water flushing 3～obtain cleaned Ti sheet for 4 times；By the NaOH that 15～25mL concentration are 1～2mol/L
Solution joins in polytetrafluoroethyllining lining autoclave, then cleaned Ti sheet is put into above-mentioned NaOH
In solution, autoclave is sealed and is placed on and the baking oven of 220～240 DEG C reacts 8～10h；After reaction terminates
Take out Ti sheet, with distilled water flushing 2～4 times, and put in drying baker and be dried, i.e. obtain and modify TiO2Nanometer
The Ti sheet of line.
Preparation method the most according to claim 2, it is characterised in that dry temperature is 50～70 DEG C.
Preparation method the most according to claim 1, it is characterised in that in step (2), liquid-phase reduction
The step of method is: the silver nitrate solution of compound concentration 0.05mol/L, with the ammonia regulation that volume fraction is 2%
Silver nitrate solution makes it occur precipitating postprecipitation disappearance, i.e. silver ammino solution, modification TiO step (1) obtained2
The Ti sheet of nano wire reacts 0.5～1h in being immersed in described silver ammino solution and being placed on the water-bath of 60～70 DEG C；Reaction
Take out Ti sheet after terminating, with distilled water flushing 2～4 times, TiO can be modified on Ti sheet2Nano wire-AgNP.
Preparation method the most according to claim 1, it is characterised in that dry temperature is 50～70 DEG C.
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